CN109761978A - A kind of near infrared fluorescent probe detecting benzenethiol and its synthetic method and application - Google Patents
A kind of near infrared fluorescent probe detecting benzenethiol and its synthetic method and application Download PDFInfo
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- CN109761978A CN109761978A CN201910046884.7A CN201910046884A CN109761978A CN 109761978 A CN109761978 A CN 109761978A CN 201910046884 A CN201910046884 A CN 201910046884A CN 109761978 A CN109761978 A CN 109761978A
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Abstract
The invention discloses a kind of near infrared fluorescent probe of highly selective detection benzenethiol and its synthetic method and applications, belong to chemical analysis detection technique field.Probe of the present invention is reacted to obtain by the big π system of dicyano isophorone-julolidine with 2,4-dinitrofluorobenzene, is had the following structure:The fluorogen of this probe is the big π system of dicyano isophorone-julolidine, and the response group to benzenethiol is 2,4- dinitrophenoxy.The probe molecule has high selectivity and sensitivity to benzenethiol, and detection range is 1-60 μm of olL‑1, detect and be limited to 0.13 μm of olL‑1.The probe can be used for the detection of water body, soil and intracellular benzenethiol.
Description
Technical field
The invention belongs to chemical analysis detection technique fields, and in particular to a kind of highly selective inspection of near-infrared trun-on type
It surveys the fluorescence probe of benzenethiol and its closes method and the application in terms of detecting benzenethiol.
Background technique
Benzenethiol (C6H5SH, PhSH) it is a kind of aromatic yl sulfide with high reaction activity, have in compound probability wide
General application, such as sulfa drugs, pesticide and high molecular synthesis.Benzenethiol has very high toxicity, breathing but then
And the intake of skin will lead to various illnesss, such as expiratory dyspnea, myasthenia, central nervous system injury are even dead.U.S.'s occupation peace
Full health office defines that the working environment maximum concentration of benzenethiol is 0.1ppm.With benzenethiol a large amount of industrial applications discharge and
Toxic action, developing highly sensitive, high selection detection benzenethiol method is very important to environment measuring and protection.
Based on molecular probe fluorescence method inspection method have sample treatment it is succinct, it is low in cost and it is easy to operate quickly etc. it is excellent
Point, is developed in recent years and utilizes.But the fluorescent probe molecule for detecting benzenethiol developed at present largely emits
Small (the Zhang W.J.Dyes and Pigments of stokes displacement value of the wavelength not in near-infrared region or probe
2016,133,248；Pagidi S.Langmuir 2018,34,8170；Genga Y.Sensors&Actuators:
B.Chemical 2018,273,1670.), since the light compared with short-wave band is weak to biological penetration capacity and there are biological damage,
And small stokes displacement value can bring the interference of exciting light, therefore, it is dry that this kind of probe molecule is unfavorable for complex sample background
The elimination disturbed, to be unfavorable for the detection of complex environment sample and biological sample.And it is close with larger stokes displacement value
Infrared fluorescence probes can overcome the above problem well.
Summary of the invention
For above situation, it is an object of the present invention to provide it is a kind of it is easily prepared, performance is stable, has larger Stokes position
The novel near-infrared fluorescent molecular probe of shifting value, and the synthetic method of the probe is provided, also go out in this foundational development to benzenethiol
Carry out highly selective and highly sensitive detection method.
Purpose to realize the present invention, the present invention have stronger necleophilic reaction characteristic using benzenethiol, can be with electron deficient point
Son or group react, and reacting for specificity can occur with benzenethiol for 2,4- dinitrodiphenyl ethers, and this patent uses 2,4- bis-
Nitro phenylate is the response group of benzenethiol.On the other hand, the big π system of dicyano isophorone-julolidine has good
Long wavelength's fluorescent emission performance, and the push-and-pull of former fluorescent molecule can be changed by introducing different electron-withdrawing groups in phenolic hydroxyl group position
For the characteristic of electron system to change its photoluminescent property, this patent designs big pi-conjugated sliding body pastern bone frame as illuminophore, synthesis
For detecting the fluorescent molecular probe of benzenethiol.
The fluorescent molecular probe of the detection benzenethiol, structural formula are as follows:
Its synthetic reaction process is as follows:
Its synthetic method is specific as follows:
In organic solvent, alkali compounds is added, compound 2 is reacted with 2,4-dinitrofluorobenzene, after isolating and purifying
To final goal products probe molecule 1.
The organic solvent is selected from one of acetonitrile, tetrahydrofuran, dimethylformamide, N-Methyl pyrrolidone.
The alkali compounds be selected from potassium carbonate, sodium carbonate, sodium acetate, triethylamine, N, N- diisopropylcarbodiimide its
One of.
Reaction time is 2-24h.
Reaction temperature is 50-120 DEG C.
Reaction condition is still more preferably as follows:
It reacts organic solvent and is selected from acetonitrile.
Reaction base is selected from potassium carbonate.
Reaction time is 8h.
Reaction temperature is 80 DEG C.
Qualitative and quantitative determination is carried out to benzenethiol using the molecular probe, for benzene in water body, soil or biosystem
The detection of thiophenol.
When using colorimetric method or Fluorometric assay, molecular probe is dissolved in the mixing buffer solution of water and dimethyl sulfoxide
In, benzenethiol is tested.After benzenethiol is added, benzenethiol energy nucleophilic attack phenoxy group, and it is further anti-by removing
It answers, makes the phenolic hydroxyl group separate out of fluorogen, to generate strong Intramolecular electron transfer (ICT) effect, make probe solution
Absorption spectrum red shift occurs, and supervene strong near-infrared fluorescent emission characteristics.
When using Fluorometric assay, the fluorescent molecular probe is 1-60 μm of olL to the detectable concentration of benzenethiol-1, inspection
Survey is limited to 0.13 μm of olL-1。
Fluorescent probe molecule of the present invention have the advantages that following features and:
The fluorescent probe molecule is with good stability and optical property, before reacting maximum absorption wave it is a length of~550nm,
Independent solution takes on a red color, unstressed configuration transmitting；With the addition of benzenethiol, probe molecule in ultraviolet absorption peak red shift to~685nm,
Solution is blue, has strong fluorescent emission property at~730nm.
Probe molecule raw material of the present invention is easy to get, and synthetic yield is higher, and up to 86% or more, stable optical performance (is visited
Needle mother liquor can be stable storage indoors three months or more, and spectral property remains unchanged), it is highly selective and highly sensitive, to benzene
Thiophenol recognition capability is strong, and response speed is very fast, and response range is 1-60 μm of olL-1, low (the 0.13 μm of olL of detection limit-1), because
This, the type probe can be used for water body, in soil and biosystem benzenethiol detection.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy for the molecular probe that the present invention synthesizes；
Fig. 2 is the uv atlas A and fluorescence spectra B that molecular probe of the present invention reacts front and back with benzenethiol, wherein A figure
In, before 1- reaction, after 2- reaction；In B figure, before 1- reaction, after 2- reaction；
Fig. 3 is 10 μm of olL of the present invention-1Molecular probe fluorescence emission spectrogram of compound after various concentration benzenethiol is added, from a
To w, benzenethiol concentration is respectively 0,1,2,5,10,15,20,25,30,35,40,45,50,55,60,70,80,90,100,
120、150、180、100μmol·L-1, solution system is the phosphate buffer solution (H of water and dimethyl sulfoxide2O/DMSO=1/1,
V/v, 10mM, pH 7.4), abscissa is wavelength, and ordinate is fluorescence intensity.
Fig. 4 is the concentration standard curve figure of benzenethiol, i.e. 10 μm of olL-1Molecular probe of the present invention, reaction front and back exist
The linear relationship with benzenethiol concentration of fluorescent emission intensity at 730nm；Abscissa is the concentration of benzenethiol, and ordinate is fluorescence
Intensity.
Fig. 5 is molecular probe of the present invention to benzenethiol selectivity；That is 200 μm of ol are added in 10 μM of molecular probes of the present invention
L-1Different material (cysteine, glutathione, homocysteine, S2-, phenol, aniline, AcO-、ClO-、CO3 2-、F-、I-、N3 -、
NO3 -、SO3 2-) after, the variation of fluorescent emission intensity at 730nm；Abscissa is the interfering substance of test, and ordinate is that fluorescence is strong
Degree.
Fig. 6 is the imaging picture that molecular probe of the present invention detects the intracellular benzenethiol of Hela.(A, B) is the present invention point respectively
Sub- fluorescence probe (10 μm of olL-1) culture Hela light field picture and fluorescence picture；(C, D) is that molecule of the present invention is glimmering respectively
Light probe (10 μm of olL-1) and benzenethiol (50 μm of olL-1) culture Hela cell light field picture and fluorescence picture.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1: the synthesis of fluorescent molecular probe
By compound 2 (0.385g, 1mmol), K is added in 2,4-dinitrofluorobenzene (0.186g, 1mmol)2CO3(0.685g,
5mmol), 80 DEG C of reaction 8h in solvent acetonitrile (20mL).To which after reaction, vacuum distillation removes solvent, column chromatography post separation
(eluant, eluent is methylene chloride) obtains product reddish black solid 0.473g (yield: 86%).Product structure formula is as follows:
1H NMR(400Hz,CDCl3): δ 8.70 (d, J=8.1Hz, 1H), 8.05 (d, J=8.7Hz, 1H), 7.98 (d, J
=7.8Hz, 1H), 7.68 (ddd, J=32.6,20.0,11.5Hz, 5H), 7.50 (d, J=8.5Hz, 2H), 7.23 (d, J=
16.2Hz, 1H), 6.64 (d, J=8.4Hz, 2H), 2.86 (s, 6H) .MS [ESI]: m/z, calcd for [M+H]+552.22；
found522.14。
Embodiment 2: fluorescence detection of the probe to benzenethiol
Above-mentioned obtained molecular probe is dissolved in the phosphate buffer solution (H of water and dimethyl sulfoxide2O/DMSO=1/1, v/
V, 10mM, pH 7.4), it is configured to 10 μm of olL-1Probe solution.10 μ that 2mL is prepared are added in the cuvette of 3mL
mol·L-1Probe solution of the present invention, the benzenethiol for being then respectively adding various concentration uniformly mixes, test its fluorescence spectrum,
As a result as shown in Figure 3.With solution, fluorescent emission intensity maps to the concentration of benzenethiol at 730nm, and benzenethiol concentration is in 1-60 μ
mol·L-1When in range, good linear relationship (Fig. 4) is presented between the two, is able to achieve determining for benzenethiol in the concentration range
Amount detection, and solution becomes blue from red, is also applied for open hole detection.And this probe is not by some other Common materials
Influence, such as cysteine, glutathione, homocysteine, S2-, phenol, aniline, AcO-、ClO-、CO3 2-、F-、I-、N3 -、
NO3 -、SO3 2-.Under the conditions of existing for the above-mentioned chaff interferent, probe containing benzenethiol to still having good selectivity and sensitivity (figure
5)。
By cell with containing after probe culture solution culture of the present invention, benzenethiol is added, and is cultivated in the solution containing benzenethiol.
Cell fluorescence imaging can observe red fluorescence (Fig. 6).
As can be seen that the present invention is able to achieve the qualitative and quantitative analysis to benzenethiol, high sensitivity, detection is limited up to 0.13 μ
mol·L-1, and it is anti-interference strong, and it is able to achieve the detection of intracellular benzenethiol.
Claims (6)
1. a kind of fluorescent molecular probe for detecting benzenethiol, which is characterized in that structural formula is as follows:
2. the method for the fluorescent molecular probe of synthesis detection benzenethiol as described in claim 1, which is characterized in that by as follows
Method is realized:
In organic solvent, alkali compounds is added, compound 2 is reacted with 2,4-dinitrofluorobenzene, is obtained most after isolating and purifying
Whole target product probe molecule 1；
The organic solvent is selected from one of acetonitrile, tetrahydrofuran, dimethylformamide, N-Methyl pyrrolidone；
The alkali compounds be selected from potassium carbonate, sodium carbonate, sodium acetate, triethylamine, N, N- diisopropylcarbodiimide wherein it
One.
3. the synthetic method of the fluorescent molecular probe of detection benzenethiol as claimed in claim 2, which is characterized in that the reaction time
For 2-24h, reaction temperature is 50-120 DEG C.
4. the application of the fluorescent molecular probe of detection benzenethiol as described in claim 1, which is characterized in that visited using the molecule
Qualitatively or quantitatively determined for benzenethiol in water body, soil or biosystem.
5. the application of the fluorescent molecular probe of detection benzenethiol as claimed in claim 4, which is characterized in that using colorimetric method or
When fluorescence detection, the molecular probe is dissolved in the aqueous mixed solution buffer system with dimethyl sulfoxide, to water body, soil
Benzenethiol carries out quantitative detection in earth.
6. the application of the fluorescent molecular probe of detection benzenethiol as claimed in claim 4, which is characterized in that by probe and cell
It cultivates, the benzenethiol in qualitative detection cell.
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| CN110092773A (en) * | 2019-05-24 | 2019-08-06 | 赣南师范大学 | A kind of oxa anthracenes derivative and its preparation method and application |
| CN110511742A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | A kind of near infrared fluorescent probe of specific recognition hydrogen polysulfide |
| CN110615786A (en) * | 2019-07-17 | 2019-12-27 | 浙江工业大学 | Near-infrared fluorescent compound for detecting viscosity and preparation and application thereof |
| CN110642857A (en) * | 2019-09-20 | 2020-01-03 | 台州学院 | Difunctional fluorescent probe for detecting viscosity and pH, and preparation and application thereof |
| CN111138431A (en) * | 2020-01-13 | 2020-05-12 | 商丘师范学院 | Reactive fluorescent probe for detecting thiophenol and synthetic method and application thereof |
| CN111205243A (en) * | 2020-02-27 | 2020-05-29 | 山西大学 | Reagent for distinguishing and detecting thiophenol and synthetic method and application thereof |
| CN112679386A (en) * | 2021-01-26 | 2021-04-20 | 吕梁学院 | Fluorescent probe for detecting 4-methylthiophenol and preparation method thereof |
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| CN110092773A (en) * | 2019-05-24 | 2019-08-06 | 赣南师范大学 | A kind of oxa anthracenes derivative and its preparation method and application |
| CN110615786A (en) * | 2019-07-17 | 2019-12-27 | 浙江工业大学 | Near-infrared fluorescent compound for detecting viscosity and preparation and application thereof |
| CN110511742A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | A kind of near infrared fluorescent probe of specific recognition hydrogen polysulfide |
| CN110642857A (en) * | 2019-09-20 | 2020-01-03 | 台州学院 | Difunctional fluorescent probe for detecting viscosity and pH, and preparation and application thereof |
| CN110642857B (en) * | 2019-09-20 | 2020-12-01 | 台州学院 | Difunctional fluorescent probe for detecting viscosity and pH, and preparation and application thereof |
| CN111138431A (en) * | 2020-01-13 | 2020-05-12 | 商丘师范学院 | Reactive fluorescent probe for detecting thiophenol and synthetic method and application thereof |
| CN111138431B (en) * | 2020-01-13 | 2022-02-15 | 商丘师范学院 | Reactive fluorescent probe for detecting thiophenol and synthetic method and application thereof |
| CN111205243A (en) * | 2020-02-27 | 2020-05-29 | 山西大学 | Reagent for distinguishing and detecting thiophenol and synthetic method and application thereof |
| CN111205243B (en) * | 2020-02-27 | 2022-05-20 | 山西大学 | Reagent for distinguishing and detecting thiophenol as well as synthesis method and application thereof |
| CN112679386A (en) * | 2021-01-26 | 2021-04-20 | 吕梁学院 | Fluorescent probe for detecting 4-methylthiophenol and preparation method thereof |
| CN112679386B (en) * | 2021-01-26 | 2021-12-10 | 吕梁学院 | Fluorescent probe for detecting 4-methylthiophenol and preparation method thereof |
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